Catalyst, and the production and use thereof



Patented Oct. 15, 1935 UN I'T'E'D STAT ES CATALYST, AND THE PRODUCTION AND USE THEREOF John D. Zieley, Belmar, N. J assignor to Amarel Corporation, Wilmington, DeL, a corporation.

of Delaware No Drawing. Application May 25, 1932,

Serial No. 613.591

2 Claims. (01. 196-531 This invention relates to catalysts, and processes of using. the same,and with regard to: certain more specific features, to catalysts. derived from. certain naturally occurring asphaltic materials.

Among the several: objects of the invention may be noted the provision of a catalyst which is useful for ca rying out processes of hydrogenation and the like with optizmnn yields of the desired products: a catalyst which is likewise beneficial in connection with certain chemical decomposition reactions; a catalyst which has a particular field of usefulness in the treatment of petroleum and like hydrocarbons, more especially the conversion of heavier or higher boiling point hydrocarbons to hydrocarbons that are lighter or of lower boiling points, an important advantage of the catalyst for these purposes being that very little or no coke is formed even from charging stocks that ordinarily give much coke on cracking, a catalyst of the class describedwhich is derived at minimum expense from a cheap, readily obtainable natural material; and the provision of a process for obtaining a catalyst of the class described from such natural material. Other objects willv be in part obvious and in part pointed out hereinafter.

The invention. accordingly comprises the elements and combinations of elements, steps and sequence of steps, and features of composition and synthesis, which will be exemplified in the products and processes hereinafter described, and the scope of the application of which will be indicated in the following claims.

A variety of natural asphalt identified as Marie1" asphalt is found in immense beds in the island of Cuba. Mariel asphalt has heretofore been of little commercial value, largely because (1) its composition is such that no economical. quantities of utilizable hydrocarbons have been recoverable therefrom, (2) it contains too high a percentage of mineral or insoluble matter, as compared with higher types of asphalt, such as Bahia or Chambre asphalt, and (3) from an economical standpoint, it is unable to meet the competition of asphalt base crude oils in the surfacing and paving industries. Accordingly, these large deposits of Mariel asphalt, while located within an economical shipping distance of the United States markets, have remained substantially unworked- Analysis of this natural Cuban Mariel asphalt is quite difficult, on account of its complex character. It is notable, however, that the percentage of ash or mineral constituents is unusually high.

For example, a low-temperature coke prepared from raw Mariel asphalt yielded the following analysis? In addition, the raw Mariel asphalt contains hydrocarbons of such high molecular Weight as to 0 renderusua-l distillation or treatment procedures ineffective.

I have discovered that the majority of this hydrocarbon content may be removed from the Marielasphalt by a process of steam distillation. 15 Ordinary steam is not successful. For optimum results, I proceed as follows:

A charge of Mariel asphalt is placed in a retort which is then closed. superheated steam, at temperatures of the order of 1000 to 1300 F., 20 is now passed through the retort. The pressure is maintained substantially at atmospheric value. Such being the case, it will be seen that the velocity at which the superheated steam travels through the retort is exceedingly high. The high 25 velocity of the steam serves a. valuable function, namely, as quickly as" the heat of the steam causes vaporization of any part of the asphalt, that part. is. instantaneously swept out of the retort. Thus the vapor pressure of vapors distill- 30 ing from the asphalt, is at all times maintained at substantially a zero value.

-While external heating of the retort may be used, I have generally found such a procedure unnecessary, exceptv that a sufiicient amount of 35 external heat may desirably be supplied to keep the discharge end. or. the retort at. the same temperature. as. that. of. the incoming steam; in other words, external heating is desirable to an extent suficient. to. compensate for heat losses within 40 and: from the retort.

The: vaporous: products of the distillation may be collected, condensed, and fractionated as is customary in. the art. The present invention is not particularly concerned with these vaporous 45 products.

The residue remaining in the retort after the distillation is soft and friable, and may easily be removed from the retort. Complexity of the composition of this ash has rendered its analysis diflicult, but it is indicated that metallic oxides, such as iron and aluminum oxides, as well as other oxides, and silica, are present in amounts up to. the order of more or less, of the ash.

The residue just described has been found to 5.5

of the Mariel asphalt residues.

composition of the steam but also catalyzes the hydrogenation of the crude oil to a remarkable extent. The effect is that excellent yields of light hydrocarbons are obtained, with little or; no'cok ing, as hereinafter appears. In operationfthe crude oil is supplied to the retort as fast as it is carried away in hydrogenated; vaporous "form; and the process is thus continuous- I The asphalt residue also appears to be. a valuable catalyst for oxygenation reactions: such as, for example, the oxygenation (by means of air) of petroleum hydrocarbonsv to alcohols, ethers, ketones, terpenes, resins, etc.

Comparative tests have been made with residues from the distillation of other asphalts and the like as hereinbefore set forth. For example, petroleum coke was prepared from heavy refinery residuum s. This petroleum coke ex hibited none of the desirable catalyzing features Further, after attempting to use such petroleum coke as a catalyst, it was found to' have become an almost solid, hard mass within the retort, which could only be removed with great difiiculty; while the Mariel residues, after use as catalysts, remain soft and friable and are easily removed from the retort.

A notable feature of the Mariel residues, as

catalysts, is the fact that they remain substantially unchanged after numerous runs. That is, they exhibit little if any, of the phenomena identified as catalyst poisoning.

The following comparative the valuble catalytic efiect of the Mariel residues. The charge material, in each instance, was Panuco crude oil, a heavy Mexican petroleum considered to be low in value and diflicult to process. The procedure used wasthe hydrogenating procedure described briefly above.

Test N0. 1

Catalyst material: Mariel asphalt residues, prepared as residues, prepared as hereinbefore set forth.

Weight of Panuco crude charged 33 lbs. 8 oz.

Gravity of Panuco crude charged 12.0 B. Weight of total distillate recovered 29 lbs. 2 oz. Per cent. recovery 86.9% Per cent. loss (including all gases) 13.1%

The total distillate was divided into a composite condensate, weighing 18 lbs. 10 oz., and a fraction absorbed in gas oil, weighing 10 lbs. 8oz. The composite condensate, representing 55.6% of the charge, had the following distillation test runs indicate I Considering the absorbed fraction as being entirely below 392 F., a summary of the composition of distillates recovered, relative to the initial charge, is:

Fraction below 392 F 42.1%

Fraction 392 to- 635 F 30.3%

Fraction above 635 F 14.5%

Loss (including all gases) 13.1%

' Tota I Y 100.0%

' Test No. 2

Catalyst material: Petroleum coke from Sinclair coking stills.

Weight of Panuco crude charged--- 20 lbs. 8 oz. Gravity of Panuco crude charged 12.0 B. Weight of total distillate recovered- 14 lbs. 10 oz. Per centrecovery 71.6% Per cent. loss (including coke) 28.4%

- The total distillate was divided into a composite condensate, weighing 11 lbs. 4 oz.,v and a fraction. absorbed in gas oil, weighing 3 lbs. 6 oz.

The composite condensate, representing 55% of 25 the charge, had the following distillation range:

Again considering the absorbed fraction as 35 being entirely below 392 F., a summary of the composition of the distillates recovered, relative to the initial charge, is:

Fraction below 392 F 20.4% Fraction 392 F.-560 F 23.7% Fraction above 560 F 27.5% Loss (including coke) 28.4%

Total 100.0% 45 A notable feature of the above comparative tests is that, while in the Mariel run, little or no coke was formed from the charged crude oil, in the petroleum coke run, considerable of the charging stock was coked. Thus, in the Mariel 50 run, the loss percentage represents substantially entirely the fixed, combustible (and economically utilizable) gases formed, while in the petroleum coke run, the excessive percentage loss represents a large amount of relatively useless coke formed.

The above tests, when compared, demonstrate conclusively the desirable efiect obtained with Mariel asphalt residues as a catalyst in obtaining. increased yields of low boiling point hydrocarbons from high boiling point material, without coking- If complete gasification of the heavy ends is desired, as in fuel gas production, a controlled amount of air maybe introduced along with the steam. This procedure constitutes a highly economical gas-manufacturing method.

In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results attained.

As many changes could be made out the above compositions and'processes without departing from the scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense. 75

in carrying 70 I claim:

1. The process of hydrogenating a hydrocarbon material comprising maintaining said material in a hydrogen-containing atmosphere in the 5 presence of a catalyst comprising Mariel asphalt residues.

2. The process of hydrogenating oil comprising maintaining said oil in a hydrogen-contaming atmosphere in the presence of a catalyst comprising Mariel asphalt residues.

JOHN D. ZIELEY. 

